1. Field of the Invention
The present invention relates to novel polymerizable compositions, novel resins, novel crosslinked polymers, novel polyester polymers, novel polyester polymers that display improvement over Rolivsan Resins, and to novel methods for obtaining resins, and polymers.
2. Background of the Art
Polymers have been able to provide a wide range of properties and capabilities which have found tremendous outlet in the commercial markets. Polymers are used in all forms of technology from medicine, commercial and residential construction, vehicular construction, optics, imaging, protective coatings, film supports and sheeting, data storage and magnetic recording, toys, inks, adhesives, binders, structural housing for appliances and conveniences, and many other commercial areas. Each of these different fields has its own unique requirements for the performance of the polymeric materials. No one polymer can meet all of the requirements for all of the fields of potential use. For this reason, certain polymers have been developed to provide better performance within certain areas of technology. For example, polyesters (such as polyethyleneterephthalate and polyethylenenaphthalate) are preferred films supports for imaging technology, as are certain cellulose acetates. Polycarbonates are preferred polymeric materials for use with window construction and lens construction. Polyacrylates have found general utility for protective coatings, particularly weatherable and UV exposed protective coatings. Epoxy resins and acrylates have found wide acceptance as adhesive materials; silicone resins have found utility as caulking, release compositions, and moisture protective coatings and compositions. Polyamides have found utility as fabric materials, thermal adhesive and biocompatible polymers in the medical field, etc.
Even within these classes of polymers and these fields, variations in the properties of the polymer are important. Failure to understand the nature of the polymer, the actual reaction mechanisms in its polymerization, impurities and additives, reaction conditions and catalysis has led to the underutilization, underachievement or at least underappreciation of some polymer compositions.
In the 1970's and 1980's, a new class of polymer was introduced by research done in the Union of Soviet Socialist Republics by Dr. Boris A. Zaitsev at the Russian Academy of Sciences. This new class of resins was referred to in the literature as Rolivsan Resins. The resins originally were known to comprise at least about three ingredients comprising three monomers. Further advances in the resins provided for the inclusion of oligomers with the monomers. The resins were initially described as derived from compositions of monomers (M) comprising from about
1-45% by weight of:
p-(CH.sub.2.dbd.CH--C.sub.6 H.sub.4).sub.2 O, bis-(4-vinylphenyl)ether (M1 type) PA1 CH.sub.2.dbd.CH--C.sub.6 H.sub.4 --O--C.sub.6 H.sub.4 --CH(CH.sub.3)OCOC(CH.sub.3).dbd.CH.sub.2 (M2 type) methacrylic ester of 4-vinyl-4'-(1-hydroxyethyl)-diphenyl-oxide or methacrylic ester of 4-vinyl-4'-(sec-ethylol)-diphenyloxide, and PA1 (p-CH.sub.2.dbd.C(CH.sub.3)--COOCH(CH.sub.3)C.sub.6 H.sub.4).sub.2 O (M3 type) dimethacrylic ester of bis-[4-(1-hydroxyethylphenyl]ether, and PA1 oligomers. PA1 Viscosity at 25.degree. C.: 450 to 5,000 cps PA1 Refractive index, n.sub.D.sup.20 : 1.560 to 1.610 PA1 Flexural strength for glass fiber cloth laminates prepared on the basis of Rolivsan resin at 20.degree. C.: 420 to 670 Mpa PA1 wherein Q is an at least diaryl group comprising two aryl groups linked directly together or bridged by an oxygen atom, sulfur atom or alkyl group, preferably an oxygen or methyl group, PA1 R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen and lower alkyl groups (e.g., methyl, ethyl, propyl and butyl, most preferably methyl). The diols will usually be provided as compositions that comprise either: PA1 a solution of the diols, with the diols comprising more than 99% by weight of the solids of the solution, and PA1 diol which has less than 1% by weight of impurity selected from the group consisting essentially of monoaryl hydroxy (Ar--OH) or sulfhydryl (Ar--SH) compounds, especially monoaryl monohydroxy or monosulfhydryl compounds, and monoaryl dihydroxy or hydroxy-sulfhydryl compounds where only one hydroxy or sulfhydryl group is attached directly to the aryl ring. PA1 1) providing a solution comprising at least one diol having the formula EQU HO--(H.sub.3 C)R.sup.4 C--Ar--Z--Ar--CR.sup.5 (CH.sub.3)--OH, or HO--(H.sub.3 C)R.sup.4 C--Q--CR.sup.5 (CH.sub.3)--OH PA1 wherein Q is as defined above, Z is --O--, --S--, or a methine group (such as --CH.sub.2 -- or CHR.sup.0 --, where R.sup.0 is a substituent group such as lower alkyl (C1 to C4), alkoxy (C1-C4) group, phenyl group, halogen, or the like), Ar is an aromatic group (e.g., phenyl, naphthyl, furyl and the like), especially mono-ring aromatic groups, and especially phenyl groups, and R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen and lower alkyl groups (e.g., methyl, ethyl, propyl and butyl group), PA1 said solution also comprising impurities selected from the group consisting of the monoaryl hydroxy groups (as defined herein); PA1 removing at least some of said monoaryl hydroxy or sulfhydryl (mercaptan) impurities which comprise monoaryl phenolic or thiophenolic compounds. PA1 wherein Q is a diaryl group comprising two, three, four, five, six and more aryl groups linked directly as in biphenyl, or bridged by oxygen atoms or sulfur atoms, such as Ph(OPh).sub.n Ph, or Ph(SPh).sub.n Ph. PA1 R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen and lower alkyl groups (e.g., methyl, ethyl, propyl and butyl, most preferably hydrogen, so that the terminal -ol group is ##STR3## PA1 a solution of the diols, with the diols comprising more than 99% by weight dissolved material or solids of the solution, and PA1 any other diol composition which comprises less than 1% by weight of impurity selected from the group consisting essentially of monoaryl hydroxy compounds, especially monoaryl monohydroxy compounds, monoaryl phenolic or thiophenolic compounds, and monoaryl dihydroxy or hydroxy-sulfhydryl compounds where only one hydroxy or sulfhydryl group is attached directly to the aryl ring. PA1 wherein Q is as defined above and R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen and lower alkyl groups (e.g., methyl, ethyl, propyl and butyl), most preferably hydrogen, PA1 2) removing at least some of said impurities which comprise monoaryl, phenolic or thiophenolic compounds. A simple purification method comprises dissolving the diol Or diol with monoaryl phenolic or thiophenolic impurities in a solvent (e.g., low alkyl alcohol such as methanol, ethanol and propanol), adding a base or base-releasing compound to the mixture to form a salt of the monoaryl phenolic or thiophenolic compound (e.g., a phenolate salt), precipitating the diol in water or ethanol (or other convenient differentiating solvent system) and then separating a main liquor from the solution or liquor carrying the precipitate of the diol, thereby reducing the concentration of monoaryl phenolic or thiophenolic compound in the diol precipitate. The monoaryl, monohydroxy, non-phenolic compound may be separated by recrystallization in solvent, such as toluene, leaving in the case of the most preferred diol, para-HO--(H.sub.3 C)HC-Ph-O-Ph-CH(CH.sub.3)--OH, a purer diol. It is particularly desirable to remove at least 10% by weight of all monoaryl impurities (either total or with respect to a single species, e.g., the monoaryl hydroxy compounds), preferably at least 25 or 30% by weight of monoaryl phenolic or thiophenolic compounds, more preferably at least 50 or 60% by weight, still more preferably at least 75, 80 or 90% by weight, and most preferably at least 95 to 99% up to 100% by weight of the monoaryl phenolic or thiophenolic impurities. PA1 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as all p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p-(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2 CH.sub.2, p, p'-CH.sub.2.dbd.CH--Ar--Ar--CH.dbd.CH.sub.2 p-(CH.sub.2.dbd.CH--C.sub.6 H.sub.4).sub.2 O, bis-(4-vinylphenyl)ether (or its counterparts where the ether linkage is replaced with sulfur or methine group or phenyl rings are linked directly), PA1 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, e.g., CH.sub.2.dbd.CH--Ar--O--Ar--CH(CH.sub.3)OCOC(CH.sub.3).dbd.CH.sub.2 methacrylic ester of 4-vinyl-4'-(1-hydroxyethyl)-diphenyl-oxide or methacrylic ester of 4-vinyl-4'-(sec-ethylol)-diphenyloxide (or its counterparts where the ether linkage is replaced with sulfur or methine group) or bridging atom (or group) is absent, i.e., the rings are linked together directly), and PA1 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl]ether, thioether or methine, e.g., p-CH.sub.2.dbd.C(CH.sub.3)--COOCH(CH.sub.3)Ar).sub.2 O dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)phenyl]ether (or its counterparts where the ether linkage is replaced with sulfur, methyne group), or aromatic rings are linked together directly, and PA1 unsaturated oligomers which can be described mainly by the formulae: ##STR6## PA1 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p-(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2 CH.sub.2, p,p'-CH.sub.2.dbd.CH--Ar--Ar--CH.dbd.CH.sub.2 p-(CH.sub.2.dbd.CH--Ar).sub.2 O, bis-(4-vinylphenyl) ether (or its counterparts where the ether linkage is replaced with sulfur or methine group), and PA1 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, e.g., CH.sub.2.dbd.CH--Ar--O--Ar--CH(CH.sub.3)OCOC(CH.sub.3).dbd.CH.sub.2 4-vinyl-4'-(1-hydroxyethyl)diphenyloxide or methacrylic ester of 4-vinyl-4'-(sec-ethylol)diphenyloxide (or its counterparts where the ether linkage is replaced with sulfur or methine group), or bridging atom (or group) is absent, i.e., the rings are linked together directly, and PA1 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, e.g., (p-CH.sub.2.dbd.C(CH.sub.3)--COOCH(CH.sub.3)Ar).sub.2 O dimethacrylic acid esters of bis-[4-(1-hydroxyethylphenyl] ether (or its counterparts where the ether linkage is replaced with sulfur, methyne group), or aromatic rings are linked together directly, and PA1 unsaturated oligomers which can be described mainly by the formulae (I) and/or (II). PA1 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p=(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2 CH.sub.2, p,p'-CH.sub.2.dbd.CH--Ar--Ar--CH.dbd.CH.sub.2, e.g., p-(CH.sub.2.dbd.CH--Ar).sub.2 O, bis-(4-vinylphenyl) ether (or its counterparts where the ether linkage is replaced with sulfur or methine group), and PA1 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, e.g., CH.sub.2.dbd.CH--Ar--O--Ar--CH(CH.sub.3)OCOC(CH.sub.3).dbd.CH.sub.2 4-vinyl-4'-(1-hydroxyethyl)diphenyloxide or methacrylic ester of 4-vinyl-4'-(sec-ethylol)diphenyloxide (or its counterparts where the ether linkage is replaced with sulfur or methine group), or bridging atom (or group) is absent, i.e., the rings are linked together directly, and PA1 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, e.g., (p-CH.sub.2.dbd.C(CH.sub.3)--COOCH(CH.sub.3)Ar).sub.2 O dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)phenyl] ether (or its counterparts where the ether linkage is replaced with sulfur, methyne group), or aromatic rings are linked together directly, and PA1 unsaturated oligomers which may be described mainly by the formulae (I) and/or (II): PA1 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p-(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2 CH.sub.2, p,p'-CH.sub.2.dbd.CH--Ar--Ar--CH.dbd.CH.sub.2, e.g., p-(CH.sub.2.dbd.CH--Ar).sub.2 O, bis-(4-vinylphenyl) ether (or its counterparts where the ether linkage is replaced with sulfur or methine group), and PA1 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, e.g., CH.sub.2.dbd.CH--Ar--O--Ar--CH(CH.sub.3)OCOC(CH.sub.3).dbd.CH.sub.2 4-vinyl-4'-(1-hydroxyethyl)diphenyloxide or methacrylic ester of 4-vinyl-4'-(sec-ethylol) diphenyloxide (or its counterparts where the ether linkage is replaced with sulfur or methine group), or bridging atom (or group) is absent, i.e., the rings are linked together directly, and PA1 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, e.g., v (p-CH.sub.2.dbd.C(CH.sub.3)--COOCH(CH.sub.3)Ar).sub.2 O dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)phenyl] ether (or its counterparts where the ether linkage is replaced with sulfur, methyne group), or aromatic rings are linked together directly, and PA1 unsaturated oligomers which may be described mainly by the formulae (I) and/or (II): 3.1 A method for obtaining these compositions comprises heating the diols (D) with carboxylic acids (CA) (with mole ratio D:CA not less than 1:0.5, preferably 1:1, or more) in the presence of relatively the lowest concentration of sulfonic acid, preferably TSA (mainly 2-10 mmole/L) in aromatic solvent (avoiding benzene), preferably toluene or o-xylene, at the boiling temperature of the solvent, preferably 110-144.degree. C. while removing the reaction water evolving during the condensation process. PA1 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p-(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2 CH.sub.2, p,p'-CH.sub.2.dbd.CH--Ar--Ar--CH--CH.sub.2, e.g., p-(CH.sub.2.dbd.CH--Ar).sub.2 O, bis-(4-vinylphenyl) ether (or its counterparts where the ether linkage is replaced with sulfur or methine group), or aromatic rings are linked together directly, and PA1 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, e.g., CH.sub.2.dbd.CH--Ar--O--Ar--CH(CH.sub.3)OCOC(CH.sub.3).dbd.CH.sub.2 4-vinyl-4'-(1-hydroxyethyl)diphenyloxide or methacrylic ester of 4-vinyl-4'-(sec-ethylol)diphenyloxide (or its counterparts where the ether linkage is replaced with sulfur or methine group), or bridging atom (or group) is absent, i.e., the rings are linked together directly. PA1 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, e.g., (p-CH.sub.2.dbd.C(CH.sub.3)--COOCH(CH.sub.3)Ar).sub.2 O dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)phenyl] ether (or its counterparts where the ether linkage is replaced with sulfur, methyne group), or aromatic rings are linked together directly, PA1 unsaturated oligomers which may be described mainly by the formula (III): ##STR8## PA1 aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic rings, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p-(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2, p,p'-CH.sub.2.dbd.CH--Ar--Ar--CH.dbd.CH.sub.2, bis-(4-vinylphenyl) ether (or its counterparts or related compounds where the ether linkage is replaced with sulfur, methylene (or methine) group or it is absent where vinylaryl group is directly linked together, and PA1 unsaturated dimer of said divinylaromatic monomer, such as p-CH.sub.2.dbd.CH--Ar--CH(CH.sub.3)--CH.dbd.CH--Ar--CH.dbd.CH.sub.2, PA1 unsaturated trimer of said divinylaromatic monomer, such as ##STR9## PA1 unsaturated tetramer and oligomer homologs of said divinylaromatic monomer, such as ##STR10## PA1 aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic ring, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p-(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2 CH.sub.2, p,p'-CH.sub.2.dbd.CH--Ar--Ar--CH.dbd.CH.sub.2, e.g. bis-(4-vinylphenyl) ether (or its counterparts or related compounds where the ether linkage is replaced with sulfur, methylene (or methine) group or it is absent where vinylaryl group is directly linked together, and PA1 unsaturated dimer of said divinylaromatic monomer, such as p-CH.sub.2.dbd.CH--Ar--CH(CH.sub.3)--CH.dbd.CH--Ar--CH.dbd.CH.sub.2, and PA1 unsaturated trimer of said divinylaromatic monomer, such as ##STR11## PA1 unsaturated tetramer and higher oligomer homologs of said divinylaromatic monomer, such as ##STR12## PA1 aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic ring, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, such as p-(CH.sub.2.dbd.CH--Ar).sub.2 O, p(CH.sub.2.dbd.CH--Ar).sub.2 S, p-(CH.sub.2.dbd.CH--Ar).sub.2 CH.sub.2, p,p'-CH.sub.2.dbd.CH--Ar--Ar--CH.dbd.CH.sub.2, e.g., bis-(4-vinylphenyl) ether (or its counterparts or related compounds where the ether linkage is replaced with sulfur, methylene (or methine) group or it is absent where vinylaryl group is directly linked together, PA1 unsaturated dimer of said divinylaromatic monomer, such as p-CH.sub.2.dbd.CH--Ar--CH(CH.sub.3)--CH.dbd.CH--Ar--CH.dbd.CH.sub.2, PA1 unsaturated timer of said divinylaromatic monomer, such as ##STR14## PA1 unsaturated tetramer and higher oligomer homologs of said divinylaromatic monomer, such as ##STR15## PA1 Other applications: sealing compounds for electronics and electro-technics (transformers, windings, condensers). PA1 The objective: The creation of the impregnating polymer compounds having:
2-35% by weight of:
5-30% by weight of:
5-88% by weight of:
The oligomers which were also described in the literature as possibly being present within the compositions (resulted from acid-catalyzed repeated dimerization and co-dimerization reactions of M1 with itself and M2) were described as having different formulae, e.g.: ##STR1## Y.dbd.CR.dbd.CH.sub.2, or --CH(CH.sub.3)OCOC(CH.sub.3).dbd.CH.sub.2,
and ##STR2## EQU Ar.dbd.C.sub.6 H.sub.4 --O--C.sub.6 H.sub.4,
and EQU n=0-3
The objective of this class of resins was to provide easy processing for high temperature resistant thermosetting resins and advanced composites. The resin reaction mixtures were provided as solvent-free compositions having viscosity ranges of from 600 up to 5,000 cps at room temperature, with melting points between 5 and 50.degree. C. for the uncured resins. The resins were to provide excellent chemical resistance to the most aggressive chemical materials (e.g., organic solvents, strong acids, alkalis, hydrazine and solutions of hydrofluoric acid). The resins were also to provide high-temperature (300.+-.50.degree. C.) performance properties and advanced composite reinforced plastics (e.g., fiberglass, polyamide and polyimide fiber, graphite, and tungsten-reinforced plastics). The resins were also to have mixing compatibility with conventional reactive resins and oligomers such as epoxy resins, unsaturated polyester resins, vinylester resins, and bis-maleimide resins. The Rolivsan Resins were also expected to exotherm in the presence of phenols, condensing with them quite readily (alkylating phenols by ethylenically unsaturated ingredients of Rolivsan Resins) at room temperature in the presence of acidic catalysts (strong acids).
An essential precursor for obtaining Rolivsan resins was bis-[4-(1-hydroxyethyl)phenyl]ether (referred to as BHEPE). The BHEPE had been obtained by the catalytic hydrogenation of bis-(4-acetyl)phenyl ether (BAPE), for example on a Raney-Nickel catalyst at conditions varying from room temperature (at high pressure) to 40 to 50.degree. C. with a hydrogen pressure of 100 atmospheres for 0.5 to 1 hour in ethyl alcohol followed by recrystallization from toluene or benzene (mp 86.degree. C.).
The Rolivsan Resins were formed by heating the BHEPE (which have been found by the present inventors to have comprised uncontrollable amounts (.about.5.+-.3%) of a phenolic impurity) with unsaturated carboxylic acids (e.g., methacrylic acid) in the presence of the considerable amounts (2.5% of BHEPE weight) of acid catalysts (such as p-toluenesulfonic acid monohydrate) in an aromatic solvent at its boiling temperature in the presence of considerable amounts (&gt;1% of BHEPE weight) of hydroquinone. It has been found by Applicant in the background of the present invention that the synthetic procedure for the production of intermediates (precursors) for the resins, especially in the synthesis of the diols which are then converted to the ethylenically unsaturated monomeric and oligomeric components of the resin, formed by-product impurities. These impurities have been found by the present inventors to produce heretofore unknown active effects on the properties and performance of the resulting resin and prevent the diols and their polymerizably active products of their transformations from use in other fields where purity might be even more critical. Some of these impurities were carried through to the final resin composition, even where standard purification techniques were used, because the physical properties of the impurities did not substantially differentiate the properties of the objective compounds.
According to the method for the manufacture of BHEPE, the basis of the pilot scale production of bis-[4-(1-hydroxyethyl)phenyl]ether (BHEPE) was by hydrogenation of bis-(4-acetyl)phenyl ether (BAPE) in the presence of Raney-nickel catalyst in processes exemplified by the following description (with variations in temperatures and pressures and time as noted herein): in Examples 1-6, in the section of EXAMPLES below.
These examples illustrate that the previously published and commercially used procedures had operated with quite high concentrations of acidic catalyst (p-toluenesulfonic acid) (2.5 to 28% of BHEPE weight) and hydroquinone (1 to 2% of BHEPE weight), and the products retained an extra-amount of the phenolic compounds as unremoved impurities in the BHEPE.
As a result, according to the Soviet Union technical (standard) specifications for the Rolivsan MV-1 resin manufacture (TU-6-14-24-62-79, valid from Jul. 20, 1979 for one ton production, and, more recently, TU 6-36-57-0-91 (instead of the previous TU-6-14-24-143-85) from Feb. 15, 1991 to Feb. 15, 1994) (Zaitsev, B. A. et al., Rolivsans--New Binders for Heat-Resistant and Strong Reinforced Plastics, Mechanics of Composite Materials, 18(5):512-515 (1982); Zaitsev, B. A. et al., Heat stable Polymer Material Rolivsan MV-1, Plast. Massy, 9:12-13 (1981)), the physical properties of uncured resin and mechanical characteristics of materials (glass fiber cloth laminates) could be uncontrollably changed in the following extremely wide range:
It can be seen that Rolivsan resins have not provided the low range of viscosity and the intended viscosity (less than 300 cps at 25.degree. C., especially less than 200 at 25.degree. C., or about 100 cps at RT) that was very important for some uses, such as polymer coatings, filled polymer compositions, reactive diluents, crosslinking agents, impregnating and sealing compounds, etc. This drawback has been due to high extent of generalization of the previously proposed method for the synthesis of resins that did not provide the controllable ratio of monomeric esters and (di)vinylaromatic monomers to unsaturated oligomers, the intended structure, amount (content), and molecular weight (and molecular weight distribution) of oligomeric component. The needed characteristics are provided with a number of proper (differentiating) methods of the present invention for obtaining novel resins having various compositions with a quite controllable, more narrow intended parameters and properties.
Another disadvantage of Rolivsan resins and their method of preparation is related to their very low and uncontrollable reactivity in three dimensional free radical (co)polymerizations as the most usable method for the cure of unsaturated monomers and oligomers. It can be seen from technical specifications that their gelation time was very long (0.5 to 1.5 hr at 140-150.degree. C.). It implies that only high temperature cure schedules could be applied for preparing polymer materials and composites.
Another disadvantage of the prior method for obtaining Rolivsan resins and related resins was in underestimating and not comprehending the effect of the acidic catalyst nature, its concentration and temperature-time schedule in the resin synthesis on structure and amount of the forming oligomeric component, and the composition of the resin on the whole.
These drawbacks had strongly limited the scope of applications of Rolivsan resins and related resins. The main reason for this behavior and properties was in the disadvantage of the method developed for their preparation. The method did not also take into account of occurring the alkylation reaction between unsaturated components (formed in the course of the resin's synthesis) and phenolic compounds both placed in the initial reaction mixture specifically as inhibitors (e.g., hydroquinone) for preventing thermal polymerization of monomers and oligomers, and being carried through the reaction along with the main reactant (BHEPE). These comprised the above-mentioned inconspicuous and unremoved diol impurities (in part resulting from a side-reaction of hydrogenolysis during the hydrogenation of BAPE for BHEPE synthesis).